Cyclopentaphenanthrenyl metal complexes and polymerization process

ABSTRACT

Group 4 metal complexes comprising a cyclopentaphenanthreneyl ligand, catalytic derivatives thereof and their use as olefin polymerization catalysts, especially for the copolymerization of ethylene and a vinylaromatic monomer are disclosed. The resulting copolymers are uniform, pseudo-random copolymers of ethylene and a vinylaromatic monomer having a cluster index, CI ES  less than 1.0 and a polymerized vinylaromatic monomer content less than 50 mole percent.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. Ser. No.09/122,958, filed Jul. 27, 1998, allowed, now U.S. Pat. No. 6,150,297issued Nov. 21, 2000 which claims benefit of priority from provisionalapplication serial No. 60/059,000, filed Sep. 15, 1997, the teachings ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to a class of Group 4 metal complexes and topolymerization catalysts derived therefrom that are particularlysuitable for use in a polymerization process for preparing homopolymersand copolymers of olefins or diolefins, including copolymers comprisingtwo or more olefins or diolefins such as copolymers comprising amonovinyl aromatic monomer and ethylene. In addition, the catalystsuniquely prepare new polymeric products having desirable physicalproperties.

Constrained geometry metal complexes and methods for their preparationare disclosed in U.S. Pat. No. 5,703,1870. This publication also teachesthe preparation of certain novel copolymers of ethylene and a hinderedvinyl monomer, including monovinyl aromatic monomers, having apseudo-random incorporation of the hindered vinyl monomer therein.Additional teachings of constrained geometry catalysts may be found inU.S. Pat. No. 5,321,106; 5,721,185, 5,374,696, 5,470,993, 5,541,349, and5,486,632, as well as WO97/15583, and WO97/19463. The teachings of allof the foregoing patents or the corresponding equivalent U.S. patentapplications are hereby incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an ORTEP drawing based on single crystal X-ray data of thecompound of Example 3.

FIG. 2 is the ¹H NMR spectrum of the ES copolymer of run 5.

SUMMARY OF THE INVENTION

According to the present invention there are provided metal complexescorresponding to the formula: CpZMX_(x)L_(I)X′_(x′)(IA);

where Cp is a cyclopentaphenanthrenyl ring system ligand optionallysubstituted

with one or more ligand groups selected from hydrocarbyl, silyl, germyl,halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylenephosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl ligand groups, said ligandgroup having up to 40 atoms not counting hydrogen atoms, and optionallytwo or more of the foregoing ligand groups may together form a divalentderivative, and further optionally one or more carbons of thecyclopentaphenanthrenyl ring system may be replaced by a nitrogen orphosphorus atom;

M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidationstate;

Z is either a cyclic or noncyclic ligand group containing delocalizedπ-electrons, including a second cyclopentaphenanthrenyl ring systemgroup as herein previously disclosed for Cp, said Z being bonded to M bymeans of delocalized π-electrons and optionally covalently bonded to Cpthrough a divalent bridging group, or Z is a divalent moiety lacking indelocalized π-electrons that is covalently bonded to Cp and M, or such amoiety comprising one σ-bond by which it is bonded to Cp, and a neutraltwo electron pair able to form a coordinate-covalent bond to M, said Zcomprising boron, or a member of Group 14 of the Periodic Table of theElements, and also comprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms other thanhydrogen;

L independently each occurrence is a neutral ligating compound having upto 20 atoms;

X′ is a divalent anionic ligand group having up to 60 atoms;

x is 0, 1, 2, or 3;

I is a number from 0 to 2, and

x′ is 0 or 1.

The above complexes may exist as isolated crystals optionally in pureform, or as a mixture with other complexes, in the form of a solvatedadduct, optionally in a solvent, especially an organic liquid, as wellas in the form of a dimer or chelated derivative thereof, wherein thechelating agent is an organic material such asethylenediaminetetraacetic acid (EDTA).

Also, according to the present invention, there is provided a catalystfor olefin polymerization comprising:

A. 1) a metal complex of formula (IA), and

2) an activating cocatalyst,

the molar ratio of 1) to 2) being from 1:10,000 to 100:1, or

B. the reaction product formed by converting a metal complex of formula(IA) to an active catalyst by use of an activating technique.

Further according to the present invention there is provided a processfor the polymerization of olefins comprising contacting one or moreC₂₋₂₀ α-olefins. under polymerization conditions with a catalystcomprising:

A. 1) a metal complex of formula (IA), and

2) an activating cocatalyst,

the molar ratio of 1) to 2) being from 1:10,000 to 100:1, or

B. the reaction product formed by converting a metal complex of formula(IA) to an active catalyst by use of an activating technique.

Use of the present catalysts and processes is especially efficient inproduction of olefin homopolymers, copolymers of two or more olefins, inparticular, copolymers of ethylene and a vinylaromatic monomer, such asstyrene, and interpolymers of three or more polymerizable monomers overa wide range of polymerization conditions, and especially at elevatedtemperatures. They are especially useful for the formation of ethylenehomopolymers, copolymers of ethylene and one or more higher α-olefins(i. e., olefins having 3 or more carbon atoms), copolymers of ethylene,propylene and a diene (EPDM copolymers), copolymers of ethylene andvinylaromatic monomers such as styrene (ES polymers), copolymers ofethylene, styrene, and a diene (ESDM polymers), and copolymers ofethylene, propylene and styrene (EPS polymers). Examples of suitablediene monomers include ethylidenenorbornene, 1,4-hexadiene or similarconjugated or nonconjugated dienes.

The ES polymers generated using certain of the present catalystcompositions are additionally remarkable due to the fact that theypossess a novel physical structure characterized by regular, homogeneousincorporation of vinylaromatic monomer into the polymer chain, comparedto conventional ES polymers in which the vinylaromatic monomer tends tobe incorporated in clusters of alternating comonomers. Such polymerspossess lower peak melting points and glass transition temperatures (Tg)at comparable compositions, polymer molecular weights and molecularweight distributions compared to previously known ES polymers.

The catalysts of this invention may also be supported on a supportmaterial and used in olefin polymerization processes in a slurry or inthe gas phase. The catalyst may be prepolymerized with one or moreolefin monomers in situ in a polymerization reactor or in a separateprocess with intermediate recovery of the prepolymerized catalyst priorto the primary polymerization process.

DETAILED DESCRIPTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1995. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups.

Cyclopentaphenanthreneyl ring system ligands, Cp, occur in severalisomeric arrangements of the various rings, conventionally indicated byuse of an italicized letter in the name. All of the known non-equivalentisomeric forms (indicated as the a, b, c and l forms) are suitable foruse herein. Preferred cyclopentaphenanthrenyl ring system ligand arethose base on cyclopenta[c]phenanthreneyl or cyclopenta[/]phenanthrenylgroups.

Preferred metal complexes according to the present invention correspondto the formula are 1H-cyclopenta[/]-phenanthreneyl metal complexescorresponding to the formula:

where M is titanium, zirconium or hafnium in the +2, +3 or +4 formaloxidation state;

R¹ independently each occurrence is hydrogen, hydrocarbyl, silyl,germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino,di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substitutedhydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R¹ group having up to40 atoms not counting hydrogen atoms, and optionally two or more of theforegoing adjacent R¹ groups may together form a divalent derivativethereby forming a saturated or unsaturated fused ring, and furtheroptionally one or more of the carbons of any of the rings may bereplaced by a nitrogen or sulfur atom;

Z is a divalent moiety lacking in delocalized π-electrons, or such amoiety comprising one σ-bond and a neutral two electron pair able toform a coordinate-covalent bond to M, said Z comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic ligand groups bound to M throughdelocalized π-electrons;

L independently each occurrence is a neutral ligating compound having upto 20 atoms;

X′ is a divalent anionic ligand group having up to 60 atoms;

x is 0, 1, 2, or 3;

I is a number from 0 to 2, and

x′ is 0 or 1.

In the metal complexes, preferred L groups are carbon monoxide;phosphines, especially trimethylphosphine, triethylphosphine,triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR⁴)₃,wherein R⁴ is C₁₋₂₀ hydrocarbyl; ethers, especially tetrahydrofuran;amines, especially pyridine, bipyridine, tetramethylethylenediamine(TMEDA), and triethylamine; olefins; and neutral conjugated dieneshaving from 4 to 40, preferably 5 to 40 carbon atoms. Complexesincluding such neutral diene L groups are those wherein the metal is inthe +2 formal oxidation state.

Further in reference to the metal complexes, X preferably is selectedfrom the group consisting of hydro, halo, hydrocarbyl, silyl, andN,N-dialkylamino-substituted hydrocarbyl. The number of X groups dependson the oxidation state of M, whether Z is divalent or not and whetherany neutral diene groups or divalent X′ groups are present. The skilledartisan will appreciate that the quantity of the various substituentsand the identity of Z are chosen to provide charge balance, therebyresulting in a neutral metal complex. For example, when Z is divalent,and x is zero, x′ is two less than the formal oxidation state of M. WhenZ contains one neutral two electron coordinate-covalent bonding site,and M is in a formal oxidation state of +3, x may equal zero and x′equal 1, or x may equal 2 and x′ equal zero. In a final example, if M isin a formal oxidation state of +2, Z may be a divalent ligand group,whereupon x and x′ are both equal to zero and one neutral L ligand groupmay be present.

Cyclopentaphenanthreneyl ligands are known ligands or may be readilyprepared from known compounds by one skilled in the art, using publishedtechniques or techniques analogous to published techniques. For example,1H-cyclopenta[/]phenanthrene which corresponds to the formula:

is a known compound. It, as well as the corresponding lithium salt,1H-cyclopenta[/]-phenanthrene-2-yl, were disclosed in J. Org. Chem.(54), 171-175 (1989).

More preferred cyclopentaphenanthrenyl ring system ligand metalcomplexes used according to the present invention are1H-cyclopenta[/]phenanthrene-2-yl complexes corresponding to theformula:

wherein:

M is titanium;

R¹ each occurrence is hydrogen or a hydrocarbyl, amino oramino-substituted hydrocarbyl group of up to 20 atoms other thanhydrogen;

Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;

Z′ is SiR⁵ ₂, CR⁵ ₂, SiR⁵ ₂SiR⁵ ₂, CR⁵ ₂CR⁵ ₂, CR⁵═CR⁵, CR⁵ ₂SiR⁵ ₂,BR⁵, or GeR⁵ ₂;

R⁵ each occurrence is independently hydrogen, or a member selected fromhydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl,and combinations thereof, said R⁵ having up to 20 non-hydrogen atoms,and optionally, two R⁵ groups from Z′ (when R⁵ is not hydrogen), or anR⁵ group from Z′ and an R⁵ group from Y form a ring system;

X, L, and X′ are as previously defined;

x is 0, 1 or 2;

I is 0 or 1; and

x′ is 0 or 1;

with the proviso that:

when x is 2, x′ is zero, M is in the +4 formal oxidation state (or M isin the +3 formal oxidation state if Y is —NR⁵ ₂ or —PR⁵ ₂), and X is ananionic ligand selected from the group consisting of halide,hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido,di(hydrocarbyl)phosphido, hydrocarbylsulfido, and silyl groups, as wellas halo-, di(hydrocarbyl)amino-, hydrocarbyloxy-, anddi(hydrocarbyl)phosphino-substituted derivatives thereof, said X grouphaving up to 30 atoms not counting hydrogen,

when x is 0 and x′ is 1, M is in the +4 formal oxidation state, and X′is a dianionic ligand selected from the group consisting ofhydrocarbadiyl, oxyhydrocarbylene, and hydrocarbylenedioxy groups, saidX group having up to 30 nonhydrogen atoms,

when x is 1, and x′ is 0, M is in the +3 formal oxidation state, and Xis a stabilizing anionic ligand group selected from the group consistingof allyl, 2-(N,N-dimethylamino)phenyl,2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethylamino)benzyl, and

when x and x′ are both 0, I is 1, M is in the +2 formal oxidation state,and L is a neutral, conjugated or nonconjugated diene, optionallysubstituted with one or more hydrocarbyl groups, said L having up to 40carbon atoms and being bound to M by means of delocalized π-electronsthereof.

Most preferred metal complexes are those according to the previousformula (ID), wherein M, R′, X, L, X′, Z′, Y, x, I and x′ are aspreviously defined, with the proviso that:

when x is 2, I and x′ are both zero, M is in the +4 formal oxidationstate, and X is independently each occurrence methyl, benzyl, or halide;

when x and I are zero, x′ is one, and M is in the +4 formal oxidationstate, X′ is a 1,4-butadienyl group that forms a metallocyclopentenering with M,

when x is 1, I and x′ are zero, M is in the +3 formal oxidation state,and X is 2-(N,N-dimethylamino)benzyl; and

when x and x′ are 0, I is 1, M is in the +2 formal oxidation state, andL is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

Especially preferred coordination complexes corresponding to theprevious formula (ID) are uniquely substituted depending on theparticular end use thereof. In particular, highly useful metal complexesfor use in catalyst compositions for the copolymerization of ethylene,one or more monovinyl aromatic monomers, and optionally an α-olefin,cyclicolefin or diolefin comprise the foregoing complexes (ID) wherein Mis titanium, X is chloride or methyl, Z′ is dimethylsilandiyl, Y ist-butylamido or phenylamido, x is 2, and I and x′ are 0, or wherein M istitanium, X′ is 1,3-pentadiene, Z′ is dimethylsilandiyl, Y ist-butylamido or phenylamido, x and x′ are 0 and I is 1.

Illustrative metal complexes that may be employed in the practice of thepresent invention include:

(t-butylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,(t-butylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N, N-dimethylamino)benzyl,

(t-butylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(t-butylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(t-butylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(isopropylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(isoproptylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(isopropylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(isopropylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(isopropylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(isopropylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(benzylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(benzylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(benzylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(benzylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(benzylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(benzylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(cyclohexylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(cyclohexylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(cyclohexylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(cyclohexylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(cyclohexylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

cyclododecylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(cyclododecylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(cyclododecylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(cyclododecylamido)dimethyl(1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(t-butylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(t-butylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(t-butylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(t-butylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(isopropylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(isopropylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(isopropylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(isopropylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(isopropylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(isopropylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(benzylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(benzylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(benzylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(benzylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(benzylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(benzylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(cyclohexylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(cyclohexylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(cyclohexylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(cyclohexylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(cyclohexylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(cyclododecylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(cyclododecylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(cyclododecylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(cyclododecylamido)dimethyl(1-methyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(t-butylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(t-butylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(t-butylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(t-butylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(t-butylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(t-butylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(isopropylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(isopropylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(isopropylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(isopropylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(isopropylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(isopropylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(benzylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

(benzylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(benzylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(benzylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(benzylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(benzylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(cyclohexylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)1,3-pentadiene,

(cyclohexylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N ,N-dimethylamino)benzyl,

(cyclohexylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(cyclohexylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl,

(cyclohexylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl,

(cyclododecylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(cyclododecylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(II)1,3-pentadiene,

(cyclododecylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(III)2-(N,N-dimethylamino)benzyl,

(cyclododecylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dichloride,

(cyclododecylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dimethyl, and

(cyclododecylamido)dimethyl(1,3-dimethyl-1H-cyclopenta[/]-phenanthreneyl)silanetitanium(IV)dibenzyl.

The complexes can be prepared by combining a Group 4 metal tetrahalideor tetraamide salt with the corresponding cyclopentaphenanthrenyl ringsystem ligand dianion in an inert diluent. Optionally a reducing agentcan be employed to produce the lower oxidation state complexes, andstandard ligand exchange procedures can by used to produce differentligand substituents. Processes that are suitably adapted for use hereinare well known to synthetic organometallic chemists. The syntheses arepreferably conducted in a suitable noninterfering solvent at atemperature from −100 to 300° C., preferably from −78 to 100° C., mostpreferably from 0 to 50° C. By the term “reducing agent” herein is meanta metal or compound which, under reducing conditions causes the metal M,to be reduced from a higher to a lower oxidation state. Examples ofsuitable metal reducing agents are alkali metals, alkaline earth metals,aluminum and zinc, alloys of alkali metals or alkaline earth metals suchas sodium/mercury amalgam and sodium/potassium alloy. Examples ofsuitable reducing agent compounds are sodium naphthalenide, potassiumgraphite, lithium alkyls, lithium or potassium alkadienyls; and Grignardreagents. Most preferred reducing agents are the alkali metals oralkaline earth metals, especially lithium and magnesium metal.

Suitable reaction media for the formation of the complexes includealiphatic and aromatic hydrocarbons, ethers, and cyclic ethers,particularly branched-chain hydrocarbons such as isobutane, butane,pentane, hexane, heptane, octane, and mixtures thereof; cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; aromaticand hydrocarbyl-substituted aromatic compounds such as benzene, toluene,and xylene, C₁₋₄ dialkyl ethers, C₁₋₄ dialkyl ether derivatives of(poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoingare also suitable.

The complexes are rendered catalytically active by combination with anactivating cocatalyst or by use of an activating technique. Suitableactivating cocatalysts for use herein include polymeric or oligomericalumoxanes, especially methylalumoxane, triisobutyl aluminum modifiedmethylalumoxane, or isobutylalumoxane; neutral Lewis acids, such asC₁₋₃₀ hydrocarbyl substituted Group 13 compounds, especiallytri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds andhalogenated (including perhalogenated) derivatives thereof, having from1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group,more especially perfluorinated tri(aryl)boron compounds, and mostespecially tris(pentafluorophenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: U.S. Pat. Nos. 5,153,157,5,064,802, 5,321,106, 5,350,723, and EP-A-520,732 (equivalent to U.S.Ser. No. 07/876,268 U.S Pat. No. 5,721,185), the teachings of which arehereby incorporated by reference.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluorophenyl-borane:alumoxane arefrom 1:1:1 to 1:5:20, more preferably from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Bronsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:

(L*−H)_(d) ⁺(A)^(d−)

wherein:

L* is a neutral Lewis base;

(L*−H)⁺ is a conjugate Bronsted acid of L*;

A^(d−) is a noncoordinating, compatible anion having a charge of d−, and

d is an integer from 1 to 3.

More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433, the teachings of which areherein incorporated by reference.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:

(L*—H)⁺(BQ₄)⁻;

wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Mostpreferably, Q is each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

trimethylammonium tetrakis(pentafluorophenyl) borate,

triethylammonium tetrakis(pentafluorophenyl) borate,

tripropylammonium tetrakis(pentafluorophenyl) borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,

N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,

N,N-dimethylaniliniumtetrakis(4-(t-butyidimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,

dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,

methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

dialkyl ammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,

methyloctadecylammonium tetrakis(pentafluorophenyl) borate,

methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and

dioctadecylammonium tetrakis(pentafluorophenyl) borate;

tri-substituted phosphonium salts such as:

triphenyiphosphonium tetrakis(pentafluorophenyl) borate,

methyidioctadecylphosphonium tetrakis(pentafluorophenyl) borate, and

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;

di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl) borate,

di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and

di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate;

di-substituted sulfonium salts such as:

di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and

methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

Preferred (L*−H)⁺ cations are methyldioctadecylammonium anddimethyloctadecylammonium.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:

(Ox^(e+))_(d)(A^(d−))_(e).

wherein:

Ox^(e+) is a cationic oxidizing agent having a charge of e+;

e is an integer from 1 to 3; and

A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag^(+′) or Pb⁺². Preferredembodiments of A^(d−) are those anions previously defined with respectto the Bronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:

©⁺A⁻

wherein:

©⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is as previously defined. A preferred carbenium ion is the tritylcation, that is triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

(R⁶ ₃Si)⁺A³¹

wherein:

R⁶ is C₁₋₁₀ hydrocarbyl, and A⁻ is as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. ChemSoc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isdisclosed in U.S. Pat. No. 5,625,087, the teachings of which are hereinincorporated by reference.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433, the teachings of which are hereinincorporated by reference.

The technique of bulk electrolysis involves the electrochemicaloxidation of the metal complex under electrolysis conditions in thepresence of a supporting electrolyte comprising a noncoordinating, inertanion. In the technique, solvents, supporting electrolytes andelectrolytic potentials for the electrolysis are used such thatelectrolysis byproducts that would render the metal complexcatalytically inactive are not substantially formed during the reaction.More particularly, suitable solvents are materials that are: liquidsunder the conditions of the electrolysis (generally temperatures from 0to 100° C.), capable of dissolving the supporting electrolyte, andinert. “Inert solvents” are those that are not reduced or oxidized underthe reaction conditions employed for the electrolysis. It is generallypossible in view of the desired electrolysis reaction to choose asolvent and a supporting electrolyte that are unaffected by theelectrical potential used for the desired electrolysis. Preferredsolvents include difluorobenzene (all isomers), dimethoxyethane (DME),and mixtures thereof.

The electrolysis may be conducted in a standard electrolytic cellcontaining an anode and cathode (also referred to as the workingelectrode and counter electrode respectively). Suitable materials ofconstruction for the cell are glass, plastic, ceramic and glass coatedmetal. The electrodes are prepared from inert conductive materials, bywhich are meant conductive materials that are unaffected by the reactionmixture or reaction conditions. Platinum or palladium are preferredinert conductive materials. Normally an ion permeable membrane such as afine glass frit separates the cell into separate compartments, theworking electrode compartment and counter electrode compartment. Theworking electrode is immersed in a reaction medium comprising the metalcomplex to be activated, solvent, supporting electrolyte, and any othermaterials desired for moderating the electrolysis or stabilizing theresulting complex. The counter electrode is immersed in a mixture of thesolvent and supporting electrolyte. The desired voltage may bedetermined by theoretical calculations or experimentally by sweeping thecell using a reference electrode such as a silver electrode immersed inthe cell electrolyte. The background cell current, the current draw inthe absence of the desired electrolysis, is also determined. Theelectrolysis is completed when the current drops from the desired levelto the background level. In this manner, complete conversion of theinitial metal complex can be easily detected.

Suitable supporting electrolytes are salts comprising a cation and acompatible, noncoordinating anion, A−. Preferred supporting electrolytesare salts corresponding to the formula G⁺A⁻; wherein:

G⁺ is a cation which is nonreactive towards the starting and resultingcomplex, and

A⁻ is as previously defined.

Examples of cations, G⁺, include tetrahydrocarbyl substituted ammoniumor phosphonium cations having up to 40 nonhydrogen atoms. Preferredcations are the tetra(n-butylammonium)- and tetraethylammonium- cations.

During activation of the complexes of the present invention by bulkelectrolysis the cation of the supporting electrolyte passes to thecounter electrode and A−migrates to the working electrode to become theanion of the resulting oxidized product. Either the solvent or thecation of the supporting electrolyte is reduced at the counter electrodein equal molar quantity with the amount of oxidized metal complex formedat the working electrode. Preferred supporting electrolytes aretetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates havingfrom 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group,especially tetra(n-butylammonium)tetrakis(pentafluorophenyl) borate. Theforegoing technique has been previously disclosed in U.S. Pat. No.5,372,682, the teachings of which are hereby incorporated by reference.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is employed in large quantity, generally at least 100 timesthe quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

The catalysts, whether or not supported in any of the foregoing methods,may be used to polymerize ethylenically and/or acetylenicallyunsaturated monomers having from 2 to 100,000 carbon atoms either aloneor in combination. The monomers for use herein include aliphatic andaromatic compounds containing vinylic unsaturation, as well as cyclicunsaturated compounds such as cyclobutene, cyclopentene, and norbornene,including norbornene substituted in the 5 and 6 position with C₁₋₂₀hydrocarbyl groups, and diolefins. Also included are mixtures of suchmonomers, especially mixtures of C₂₋₈ olefins with C₄₋₄₀ diolefincompounds. Examples of the latter compounds includeethylidenenorbornene, 1,4-hexadiene, and norbornadiene. Long chain vinylterminated monomers may be formed during the polymerization process, forexample by the phenomenon of β-hydride elimination of a proton from agrowing polymer chain. This process results in incorporation of suchextremely long chains of preformed polymer into the resulting polymer,i. e. long chain branching. The catalysts and processes herein areespecially suited for use in preparation of ethylene/propylene,ethylene/1-butene, ethylene/1-hexene, ethylene/styrene, andethylene/1-octene copolymers as well as terpolymers of ethylene,propylene and a nonconjugated diene, referred to as EPDM polymers,terpolymers of ethylene, propylene and styrene, referred to as EPSpolymers, or terpolymers of ethylene, styrene and a nonconjugated diene,referred to as ESDM polymers.

Vinylaromatic monomers for use herein include C₈₋₂₀ aryl substitutedethylene compounds having the formula:

wherein:

R² independently each occurrence is hydrogen or C₁₋₄ alkyl, and

R³ independently each occurrence is R² or halo.

Preferred monomers include the C₂₋₂₀ olefins especially ethylene,propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, tetrafluoroethylene,norbornene, vinylbenzocyclobutane, ethylidenenorbornene, 1,4-hexadiene,1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene, andmixtures thereof with ethylene.

More preferred monomers include a combination of ethylene and one ormore comonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:100,000 to 1:10, more preferably from 1:50,000 to 1:20, and mostpreferably from 1:10,000 to 1:30.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

Suitable solvents use for solution polymerization are inert liquids.Examples include straight and branched-chain hydrocarbons such asisobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene.

Suitable solvents also include liquid olefins which may act as monomersor comonomers. The catalysts may be utilized in combination with atleast one additional homogeneous or heterogeneous polymerizationcatalyst in the same reactor or in separate reactors connected in seriesor in parallel to prepare polymer blends having desirable properties. Anexample of such a process is disclosed in WO 94/00500, equivalent toU.S. Ser. No. 07/904,770, now abandoned as well as U.S. Ser. No.08/010958, filed Jan. 29, 1993, now abandoned the teachings of which arehereby incorporated by reference herein.

Utilizing the present catalysts, interpolymers of ethylene, one or morevinylaromatic monomers and optionally an α-olefin or a diolefin havingdensities from 0.85 g/cm³ to 1.1 g/cm³, melt flow rates from 0.01 to20.0 dg/min, and incorporating large amounts of vinylaromatic monomer ina pseudo-random manner are readily attained in a highly efficientprocess. Pseudo-random incorporation of vinylaromatic monomers is a wellknown phenomena in which the monomer is essentially randomlyincorporated into the polymer, excepting that two such vinylaromaticmonomers having the same orientation may not succeed one another in thepolymer chain. The procedure has been previously disclosed in U.S. PatNo. 5,703,187, the teachings of which are herein incorporated byreference.

The catalysts of the present invention are also particularlyadvantageous for the production of ethylene homopolymers,ethylene/α-olefin copolymers, and interpolymers of ethylene a diene andoptionally a C₃₋₂₀ α-olefin having high levels of long chain branchingand comonomer incorporation. The use of the catalysts of the presentinvention in continuous polymerization processes, especially continuous,solution polymerization processes, allows for elevated reactortemperatures which favor the formation of vinyl terminated polymerchains that may be incorporated into a growing polymer, thereby giving along chain branch. The use of the present catalyst compositionsadvantageously allows for the economical production of ethylene/α-olefincopolymers having processability similar to high pressure, free radicalproduced low density polyethylene.

The present catalyst compositions may be advantageously employed toprepare olefin polymers having improved processing properties bypolymerizing ethylene alone or ethylene/α-olefin mixtures with lowlevels of a “H” branch inducing diene, such as norbornadiene,1,7-octadiene, or 1,9-decadiene. The unique combination of elevatedreactor temperatures, high molecular weight (or low melt indices) athigh reactor temperatures and high comonomer reactivity advantageouslyallows for the economical production of polymers having excellentphysical properties and processability. Preferably such polymerscomprise ethylene, a C₃₋₂₀ α-olefin and a “H”-branching comonomer.Preferably, such polymers are produced in a solution process, mostpreferably a continuous solution process.

The catalyst composition may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst composition may also be prepared and employedas a heterogeneous catalyst by adsorbing the requisite components on aninert inorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, trialkylaluminum compounds, andorganic or inorganic polymeric materials, especially polyolefins. In anpreferred embodiment, a heterogeneous catalyst is prepared byco-precipitating the metal complex, an inert, inorganic compound and anactivator, especially an ammonium salt of ahydroxyaryl(trispentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)(trispentafluorophenylborate. Apreferred inert, inorganic compound for use in this embodiment is a tri(C₁₋₄ alkyl) aluminum compound.

When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably at least a major part of the diluent comprises theα-olefin monomer or monomers to be polymerized.

At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas such as, for example, nitrogen.

The polymerization may be carried out as a batchwise or a continuouspolymerization process A continuous process is preferred, in which eventcatalyst, ethylene, comonomer, and optionally solvent are continuouslysupplied to the reaction zone and polymer product continuously removedtherefrom.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously together with solvent and an optional chain transfer agent.The reactor contains a liquid phase composed substantially of monomerstogether with any solvent or additional diluent and dissolved polymer.If desired, a small amount of a “H”-branch inducing diene such asnorbornadiene, 1,7-octadiene or 1,9-decadiene may also be added.Catalyst and cocatalyst are continuously introduced in the reactorliquid phase. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or both. The polymerization rateis controlled by the rate of catalyst addition. The ethylene content ofthe polymer product is determined by the ratio of ethylene to comonomerin the reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mentioned chain transfer agent, such as a stream of hydrogenintroduced to the reactor, as is well known in the art. The reactoreffluent is contacted with a catalyst kill agent such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from about 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours. By using a catalyst thatincorporates large amounts of hindered monovinyl monomer, such as avinylaromatic monomer, hindered monovinyl homopolymer formed fromresidual quantities of the monomer are substantially reduced.

As previously mentioned, the catalysts of the invention are capable ofproducing novel ES polymers. Particularly when used in a continuouspolymerization process, especially a continuous solution polymerizationprocess, the resulting ES polymer has been found to contain highlyuniform vinylaromatic monomer incorporation. Such uniform ES polymersare characterized by a unique ¹³C NMR signature. In particular, suchpolymers are characterized by a cluster index, CI_(ES), which relates aratio of two peaks in the ¹³C NMR spectrum, NMR_(F)/NMR_(E), whereinNMR_(F) is the integrated area of the peak associated only withvinylaromatic monomer/ethylene/vinylaromatic monomer (SES) triads(commonly appearing at approximately 25 to 26.9 ppm) and NMR_(E) is theintegrated area of the peak associated only with triads containing asingle incorporated vinylaromatic monomer (commonly appearing atapproximately 27 to 29 ppm). It should be emphasized that in both typesof polymers the vinylaromatic monomer is incorporated in a pseudo randommanner, that is, successive or adjacent head to tail insertion of avinyl aromatic monomer in the polymer chain is still prohibited. Suchpseudo random nature characteristically produces a ¹H NMR spectrum ofthe polymer which lacks any appreciable peaks between the two peakslocated at approximately 37 and 46 ppm respectively. However, in uniformES polymers, lack of clustering of the incorporated vinylaromaticmonomer into alternating monomer sequences can be identified bycomparing the area of the NMR_(E) peaks relative to NMR_(F) peaks as afunction of monomer composition in the polymer.

This cluster index, CI_(ES), can be expressed mathematically through useof the following formula:${CI}_{ES} = {\left\lbrack \frac{{NMR}_{F}}{{NMR}_{E}} \right\rbrack \left\lbrack \frac{\left( {{4F_{1}} - 2} \right)}{\left( {1 - F_{1}} \right)} \right\rbrack}$

where F₁ is the mole fraction of ethylene in the polymer. The uniformpseudo-random ES polymers of the invention are characterized by CI_(ES)values less than 1.0 at polymer compositions of less than 50 molepercent polymerized vinylaromatic monomer, referably CI_(ES) values lessthan 0.95 at compositions of less than 47 mole percent olymerizedvinylaromatic monomer.

The process of the present invention can be employed to advantage in thegas phase copolymerization of olefins. Gas phase processes for thepolymerization of olefins, especially the homopolymerization andcopolymerization of ethylene and propylene, and the copolymerization ofethylene with higher α-olefins such as, for example, 1-butene, 1-hexene,4-methyl-1-pentene are well known in the art. In such processes, coolingof the reactor may be provided by the use of recycle gas, which is fedas a volatile liquid to the bed to provide an evaporative coolingeffect. The volatile liquid employed in this case can be, for example, avolatile inert liquid, for example, a saturated hydrocarbon having 3 to8, preferably 4 to 6, carbon atoms. In the case that the monomer orcomonomer itself is a volatile liquid (or can be condensed to providesuch a liquid) this can be fed to the bed to provide an evaporativecooling effect. Examples of olefin monomers which can be employed inthis manner are olefins containing three to eight, preferably three tosix carbon atoms. The volatile liquid evaporates in the hot fluidizedbed to form gas which mixes with the fluidizing gas. If the volatileliquid is a monomer or comonomer, it will undergo some polymerization inthe bed. The evaporated liquid then emerges from the reactor as part ofthe hot recycle gas, and enters the compression/heat exchange part ofthe recycle loop. The recycle gas is cooled in the heat exchanger and,if the temperature to which the gas is cooled is below the dew point,liquid will precipitate from the gas. This liquid is desirably recycledcontinuously to the fluidized bed. It is possible to recycle theprecipitated liquid to the bed as liquid droplets carried in the recyclegas stream. This type of process is described, for example in EP 89691;U.S. Pat. No. 4,543,399; WO 94/25495 and U.S. Pat. No. 5,352,749, whichare hereby incorporated by reference. A particularly preferred method ofrecycling the liquid to the bed is to separate the liquid from therecycle gas stream and to reinject this liquid directly into the bed,preferably using a method which generates fine droplets of the liquidwithin the bed. This type of process is described in WO 94/28032, theteachings of which is hereby incorporated by reference.

The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalyst.Such catalyst can be supported on an inorganic or organic supportmaterial as described above.

The polymer is produced directly in the fluidized bed by catalyzedcopolymerization of the monomer and one or more comonomers on thefluidized particles of catalyst, supported catalyst or prepolymer withinthe bed. Start-up of the polymerization reaction is achieved using a bedof preformed polymer particles, which are preferably similar to thetarget polyolefin, and conditioning the bed according to techniques thatare well known in the art. Such processes are used commercially on alarge scale for the manufacture of high density polyethylene (HDPE),medium density polyethylene (MDPE), linear low density polyethylene(LLDPE) and polypropylene.

The gas phase process employed can be, for example, of the type whichemploys a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported above a perforated plate, the fluidization grid, by a flow offluidization gas.

The gas employed to fluidize the bed comprises the monomer or monomersto be polymerized, and also serves as a heat exchange medium to removethe heat of reaction from the bed. The hot gases emerge from the top ofthe reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a larger cross-sectional area than thefluidized bed and wherein fine particles entrained in the gas streamhave an opportunity to gravitate back into the bed. It can also beadvantageous to use a cyclone to remove ultra-fine particles from thehot gas stream. The gas is then normally recycled to the bed by means ofa blower or compressor and one or more heat exchangers to strip the gasof the heat of polymerization. The produced polymer is dischargedcontinuously or discontinuously from the fluidized bed as desired.

The gas phase processes suitable for the practice of this invention arepreferably continuous processes which provide for the continuous supplyof reactants to the reaction zone of the reactor and the removal ofproducts from the reaction zone of the reactor, thereby providing asteady-state environment on the macro scale in the reaction zone of thereactor.

Typically, the fluidized bed of the gas phase process is operated attemperatures greater than 50° C., preferably from 60° C. to 110° C.,more preferably from 70° C. to 110° C.

Typically the molar ratio of comonomer to monomer used in thepolymerization depends upon the desired density for the compositionbeing produced and is 0.5 or less. Desirably, when producing materialswith a density range of from 0.91 to 0.93 the comonomer to monomer ratiois less than 0.2, preferably less than 0.05, even more preferably lessthan 0.02, and may even be less than 0.01. Typically, the ratio ofhydrogen to monomer is less than 0.5, preferably less than 0.2, morepreferably less than 0.05, even more preferably less than 0.02 and mayeven be less than 0.01.

The above-described ranges of process variables are appropriate for thegas phase process of this invention and may be suitable for otherprocesses adaptable to the practice of this invention.

A number of patents and patent applications describe gas phase processeswhich are adaptable for use in the process of this invention,particularly, U.S. Pat. No. 4,588,790; 4,543,399; 5,352,749; 5,436,304;5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670;5,473,028; 5,106,804; 5,541,270 and EP applications 659,773; 692,500;and PCT Applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032;WO 95/13305; WO 94/26793; and WO 95/07942, the teachings of all of whichare hereby incorporated herein by reference.

EXAMPLES

The skilled artisan will appreciate that the invention disclosed hereinmay be practiced in the absence of any component which has not beenspecifically disclosed. The following examples are provided as furtherillustration of the invention and are not to be construed as limiting.Unless stated to the contrary all parts and percentages are expressed ona weight basis. All syntheses were performed under dry nitrogenatmosphere using a combination of glove box and high vacuum techniques.The term “overnight” refers to a period of time from 14 to 20 hours. Theterm “room temperature” refers to a temperature from 20 to 25° C.

Example 1

Preparation of Lithium 1H-cyclopenta[/]phenanthrene-2-yl

To a 250 ml round bottom flask containing 1.42 g (0.00657 mole) of1H-cyclopenta[/]phenanthrene and 120 ml of benzene was added dropwise,4.2 ml of a 1.60 M solution of n-BuLi in mixed hexanes. The solution wasallowed to stir overnight. The lithium salt was isolated by filtration,washing twice with 25 ml benzene and drying under vacuum. Isolated yieldwas 1.426 g (97.7 percent).

Preparation of (1H-cyclopenta[/]hphenanthrene-1-yl)dimethylchlorosilane

To a 500 ml round bottom flask containing 4.16 g (0.0322 mole) ofdimethyidichlorosilane (Me₂SiCl₂) and 250 ml of tetrahydrofuran (THF)was added dropwise a solution of 1.45 g (0.0064 mole) of lithium1H-cyclopenta[/]phenanthrene-2-yl in THF. The solution was stirred forapproximately 16 hours, after which the solvent was removed underreduced pressure, leaving an oily solid which was extracted withtoluene, filtered through diatomaceous earth filter aid (Celite™),washed twice with toluene and dried under reduced pressure. Isolatedyield was 1.98 g (99.5 percent). ¹H NMR analysis indicated thepredominant isomer was substituted at the 1 position.

Preparation of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamino)silane

To a 500 ml round bottom flask containing 1.98 g (0.0064 mole) of(1H-cyclopenta[/]phenanthrene-2-yl)dimethylchlorosilane and 250 ml ofhexane was added 2.00 ml (0.0160 mole) of t-butylamine. The reactionmixture was allowed to stir for several days, then filtered usingdiatomaceous earth filter aid (Celite™), washed twice with hexane. Theproduct was isolated by removing residual solvent under reducedpressure. The isolated yield was 1.98 g (88.9 percent). ¹H NMR analysisindicated the predominant isomer was substituted at the 2 position dueto migration of the silane substituent.

Preparation of dilithio(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silane

To a 250 ml round bottom flask containing 1.03 g (0.0030 mole) of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamino)silane) and 120ml of benzene was added dropwise 3.90 ml of a solution of 1.6 M n-BuLiin mixed hexanes. The reaction mixture was stirred for approximately 16hours. The product was isolated by filtration, washed twice with benzeneand dried under reduced pressure. Isolated yield was 1.08 g (100percent).

Preparation of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDichloride

To a 250 ml round bottom flask containing 1.17 g (0.0030 mole) ofTiCl₃.3THF and 120 ml of THF was added at a fast drip rate 50 ml of aTHF solution of 1.08 g of dilithio(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silane. Themixture was stirred at 20-25° C. for 1.5 h at which time 0.55 gm (0.002mole) of solid PbCl₂ was added. After stirring for an additional 1.5 hthe THF was removed under vacuum and the reside was extracted withtoluene, filtered and dried under reduced pressure to give an orangesolid. Yield was 1.31 g (93.5 percent).

Example 2

Preparation of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDimethyl

To a 100 ml round bottom flask containing 0.480 g (0.00104 mole) of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdichloride and 50 ml of diethylether was added dropwise 0.75 ml of a 3.0M solution of MeMgBr in diethylether. The reaction mixture was allowedto stir for 0.5 h. The volatiles were removed under reduced pressure andthe residue was extracted with hexane and then filtered. The desiredproduct was isolated by removing the solvent under reduced pressure togive 0.196 g (44.8 percent yield) of a yellow solid.

Example 3

Preparation of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitanium1,4-diphenylbutadiene

To a slurry of(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdichloride (3.48 g, 0.0075 mole) (produced by scaling up Example 1) and1.551 gm (0.0075 mole) of 1,4-diphenyllbutadiene in 80 ml of toluene at70° C. was add 9.9 ml of a 1.6 M solution of n-BuLi (0.0150 mole). Thesolution immediately darkened. The temperature was increased to bringthe mixture to reflux and the mixture was maintained at that temperaturefor 2 hrs. The mixture was cooled to −20° C. and the volatiles wereremoved under reduced pressure. The residue was slurried in 60 ml ofmixed hexanes at 20-25° C. for approximately 16 hours. The mixture wascooled to −25° C. for 1 h. The solids were collected on a glass frit byvacuum filtration and dried under reduced pressure. The dried solid wasplaced in a glass fiber thimble and solid extracted continuously withhexanes using a soxhlet extractor. After 6 h a crystalline solid wasobserved in the boiling pot. The mixture was cooled to −20° C., isolatedby filtration from the cold mixture and dried under reduced pressure togive 1.62 g of a dark crystalline solid. The filtrate was discarded. Thesolids in the extractor were stirred and the extraction continued withan additional quantity of mixed hexanes to give an additional 0.46 gm ofthe desired product as a dark crystalline solid.

A sample of the product was examined by X-ray diffraction, ¹H NMRspectroscopy, ¹³C NMR spectroscopy, elemental analysis and X-raydiffraction. The ORTEP generated from the single crystal X-ray analysisis contained in FIG. 1.

Powder X-ray diffraction analysis confirmed that the sample wasrepresentative of the product.

Example 4(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDichloride

Preparation of lithium 3-methyl-1H-cyclopenta[/]phenanthrene-2-yl

To a 250 ml round bottom flask containing 1.26 g (0.00547 mole) of3-Methyl-1H-cyclopenta[/]phenanthrene and 120 ml of benzene was addeddropwise, 3.60 ml of a 1.60 M solution of n-BuLi in mixed hexanes. Thesolution was allowed to stir overnight. The lithium salt was isolated byfiltration, washing twice with 25 ml benzene and drying under vacuum.Isolated yield was 1.250 g (96.9 percent).

Preparation of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyichlorosilane

To a 500 ml round bottom flask containing 1.71 g (0.01323 mole) ofdimethyidichlorosilane (Me₂SiCl₂) and 250 ml of tetrahydrofuran (THF)was added dropwise a solution of 1.25 g (0.00529 mole) of lithium3-Methyl-1H-cyclopenta[/]phenanthrene-2-yl in 60 ml THF. The solutionwas stirred overnight, after which the solvent was removed under reducedpressure, leaving a solid which was extracted with toluene, filteredthrough diatomaceous earth filter aid (Celite™), washed twice withtoluene and dried under reduced pressure. Isolated yield was 1.699 g(97.7 percent). ¹H NMR analysis indicated the predominant isomer wassubstituted at the 1 position.

Preparation of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamino)silane

To a 500 ml round bottom flask containing 1.699 g (0.00526 mole) of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethylchlorosilane and 100ml of hexane and 150 ml toluene was added 0.975 g (0.0132 mole) oft-butylamine. The reaction mixture was allowed to stir for several days,then filtered using diatomaceous earth filter aid (Celite™), washedtwice with hexane. The product was isolated by removing residual solventunder reduced pressure. The isolated yield was 1.785 g (94.6 percent).1H NMR analysis indicated the predominant isomer was substituted at the2 position.

Preparation of dilithio(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silane

To a 500 ml round bottom flask containing 1.7785 g (0.00498 mole) of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamino)silane)and 120 ml of hexane was added dropwise 6.50 ml of a solution of 1.6 Mn-BuLi in mixed hexanes. The reaction mixture was stirred overnight. Theproduct was isolated by filtration, washed twice with hexane and driedunder reduced pressure. Isolated yield was 1.544 g (83.7 percent).

Preparation of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDichloride

To a 250 ml round bottom flask containing 1.540 g (0.00417 mole) ofTiCl₃.3THF and 130 ml of THF was added at a fast drip rate 50 ml of aTHF solution of 1.544 g of dilithio(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silane.The mixture was stirred at 20-25° C. for 1.5 h at which time 0.64 gm(0.0023 mole) of solid PbCl₂ was added. After stirring for an additional1.25 h the THF was removed under vacuum and the reside was extractedwith toluene, filtered and dried under reduced pressure to give anorange/brown solid. Yield was 0.84 g (42.3 percent).

Example 5

Preparation of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDimethyl

To a 100 ml round bottom flask containing 0.790 g (0.00147 mole) of(1-methyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdichloride and 50 ml of diethylether was added dropwise 1.03 ml of a 3.0M solution of MeMgBr in diethylether. The reaction mixture was allowedto stir for 2.0 h. The volatiles were removed under reduced pressure andthe residue was extracted with hexane and then filtered. The desiredproduct was isolated by removing the solvent under reduced pressure togive 0.480 g (75.0 percent yield) of a dirty yellow solid.

Example 6(1,3-dimethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdichloride

Preparation of Lithium 1,3-dimethyl-1H -cyclopenta[/]phenanthrene-2-yl

To a 500 ml round bottom flask containing 1.90 g (0.00781 mole) of1,3-diMethyl-1H-cyclopenta[/]phenanthrene and 2250 ml of benzene/toluenewas added dropwise, 5.36 ml of a 1.60 M solution of n-BuLi in mixedhexanes. The solution was allowed to stir overnight. The lithium saltwas isolated by filtration, washing twice with 25 ml benzene and dryingunder vacuum. Isolated yield was 1.898 g (97.5 percent).

Preparation of(1,3-dimethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyichlorosilane

To a 500 ml round bottom flask containing 4.92 g (0.0381 mole) ofdimethyldichlorosilane (Me₂SiCl₂) and 250 ml of tetrahydrofuran (THF)was added via a slow dropwise addition of a solution of 1.898 g (0.00761mole) of lithium 1,3-diMethyl-1H-cyclopentaflphenanthrene-2-yl in 60 mlTHF. The solution was stirred overnight, after which the solvent wasremoved under reduced pressure, leaving a solid which was extracted withtoluene, filtered through diatomaceous earth filter aid (Celite™),washed twice with toluene and dried under reduced pressure. Isolatedyield was 2.420 g (92.4 percent). 1H NMR analysis indicated thepredominant isomer was substituted at the 1 position.

Preparation of (1,3-dimethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamino)silane

To a 500 ml round bottom flask containing 2.420 g (0.00718 mole) of(1,3-diMethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethylchlorosilane and250 ml of methylene chloride was added 1.331 g (0.0180 mole) oft-butylamine. The reaction mixture was allowed to stir for several days,then filtered using diatomaceous earth filter aid (Celite™), washedtwice with hexane. The product was isolated by removing residual solventunder reduced pressure. The isolated yield was 2.120 g (79.0 percent).1H NMR analysis indicated the predominant isomer was substituted at the2 position.

Preparation of dilithio(1,3-dimethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silane

To a 500 ml round bottom flask containing 2.120 g (0.00567 mole) of(1,3-diMethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamino)silane)and 250 ml of hexane was added dropwise 7.8 ml of a solution of 1.6 Mn-BuLi in mixed hexanes. The reaction mixture was stirred overnight. Theproduct was isolated by filtration, washed twice with hexane and driedunder reduced pressure. Isolated yield was 1.847 g (84.7 percent).

Preparation of(1,3-dimethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDichloride

To a 500 ml round bottom flask containing 1.771 g (0.00479 mole) ofTiCl₃.3THF and 250 ml of THF was added at a fast drip rate 75 ml of aTHF solution of 1.847 g of dilithio(1,3-diMethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silane.The mixture was stirred at 20-25° C. for 1.5 h at which time 0.733 gm(0.0026 mole) of solid PbCl₂ was added. After stirring for an additional1.5 h the THF was removed under vacuum and the reside was extracted withhot toluene, cooled filtered and dried under reduced pressure to give anorange solid. Yield was 0.80 g (34.5 percent).

Example 7

Preparation of(1,3-dimethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumDimethyl

To a 100 ml round bottom flask containing 0.320 g (0.00065 mole) of(1,3-diMethyl-1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdichloride and 50 ml of diethylether was added dropwise 0.446 ml of a3.0 M solution of MeMgBr in diethylether. The reaction mixture wasallowed to stir for 2.0 h. The volatiles were removed under reducedpressure and the residue was extracted with hexane and then filtered.The desired product was isolated by removing the solvent under reducedpressure to give 0.239 g (81.6 percent yield) of a deep yellow solid.

Polymerization Examples

Ethylene/styrene Copolymerization

The polymerization conditions were as follows: A two-liter Parr reactorwas charged with approximately 360 g of Isopar-E™ mixed alkanes solvent(available from Exxon Chemicals Inc.) and 460 g of styrene comonomer.Hydrogen was added as a molecular weight control agent by differentialpressure expansion from a 75 mL addition tank at 50 psig (345 kPa). Thereactor was heated to 90° C. and saturated with ethylene at 200 psig(1.4 MPa). The appropriate amount of catalyst and cocatalyst(trispentafluorophenylborane) as 0.005M solutions in toluene(approximately 3 μmole) were premixed in a glovebox to give a 1:1 molarratio of catalyst and cocatalyst, and transferred to a catalyst additiontank and injected into the reactor. The polymerization conditions weremaintained for 30 minutes with ethylene on demand. The resultingsolution was removed from the reactor into a nitrogen purged collectionvessel containing 100 ml of isopropyl alcohol and 20 ml of a 10 weightpercent toluene solution of hindered phenol antioxidant (Irganox™ 1010from Ciba Geigy Corporation) and phosphorus stabilizer (Irgafos 168).Polymers formed are dried in a programmed vacuum oven with a maximumtemperature of 130° C. and a 20 hours heating cycle. Results are shownin Table 1.

TABLE 1 Run complex Yield (g) Efficiency¹ styrene² 1 Example 2 133.70.93 30.9 2 Example 3 202.6 1.06 30.5 3 Example 5  85.3 0.26 29.4 4Example 7 112.6 0.39 31.6 compare A TMCTP* 63  0.22 13   ¹Kg polymer/gtitanium ²mole percent styrene*(t-butylamido)dimethyl(η⁵-tetramethylcyclopentadienyl)titanium1,3-pentadiene

Continuous Polymerizations and Composition Index Calculation

Reactor

A continuous loop reactor operating under isothermal polymerizationconditions was prepared for use. The reactor loop was composed of two ½″(1.27 cm) Koch SMX static mixers, a custom, 1200 mL/min, magneticallycoupled, Micropump® gear pump and assorted ½″ (1.27 cm) Swagelok® tubefittings. The loop was equipped with two inlets, one for metered flowsof purified ethylene, hydrogen, toluene and styrene or mixtures ofstyrene and toluene, the other for the active catalyst system. Apressure transducer on the feed inlet and a dual thermocouple in theloop provided inputs for computerized control of reactor pressure andtemperature via electrical heating tapes on the static mixers and anelectrically operated control valve on the reactor outlet. An in-lineviscometer (available from Cambridge Applied Scientifics Corporation)was used to monitor the outlet flow.

Process Conditions

Styrene (with 12 ppm t-butylcatechol) and 2,4-dinitro-p-cresol (20 ppm)was placed in a 20 lb. propane cylinder, sparged with helium and thenpumped through a 1.5″×20″ (3.8×50.8 cm) column packed with activatedA-204 alumina (available from Kaiser Aluminum Co.). Toluene solvent wasstored in a 20 gallon cylinder, sparged with helium and pumped throughtwo 2″×30″ (5.1×76.2 cm) columns, one packed with activated A-2 aluminaand 3 Å molecular sieves, the other with activated oxygen reactant(available from Engelhard Corporation under the trade designation Q-5®,Cu-0226 S).

The metal complex,(1H-cyclopenta[/]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitanium1,4-diphenylbutadiene, was used as a 1.00×10⁻³ M solution in toluene.Tris(pentafluorophenyl)borane cocatalyst (FAB) was prepared as a2.00×10⁻³ M solution in toluene and was delivered to the reactor in a1:1 (by volume) mixture with the metal complex solution.

The reaction was monitored in-situ by a fiber-optic FTNIR spectrometercalibrated for various mixtures of ethylene and styrene in toluene overa broad temperature range. The measured ethylene and styreneconcentrations were used to determine conversions based on the knownfeed rates. The measured conversions were in turn used as the input forthe controller which varied the catalyst feed rate in order to maintaina conversion set point.

The polymer solution was quenched upon exiting the reactor with atoluene solution consisting of isopropyl alcohol (15 ml/l), and ahindered phenol antioxidant (0.02 g/ml). The cooled polymer solution wasplaced in a vacuum oven in which the temperature was slowly raised from40° C. to 130° C. overnight. The polymer was cooled to below 50° C.before removing it from the vacuum oven the next day.

A comparative ES copolymer was also prepared under similar continuoussolution polymerization conditions but using the metal complex(t-butylamido)dimethyl(η⁵-tetramethylcyclopentadienyl)silanetitaniumdimethyl. A 50 percent by weight highly pure solution of styrene intoluene was continuously pumped into the reactor. Hydrogen was alsoadded to the reactor. The operation parameters for the polymerizationexperiments are given in Table 2.

TABLE 2 Toluene Styrene Catalyst (mL/ (mL/ Ethylene (mL/ Temp. H₂ runmin) min) (g/min) min) ° C. (mg/min) 5 11.05 2.00 0.600 0.235 100.0 —compare B * * 0.636 0.200  60.0 0.4 *The 50 percent by weight styrenesolution in toluene was added at a rate of 12.1 ml/min

The resulting ES copolymers were pseudo random (characterized by a lackof any appreciable peaks in the ¹H NMR spectrum of the polymer betweenthe two peaks located at approximately 37 and 46 ppm respectively). Thepolymerized styrene content of the ES copolymer of run 5 and comparisonB were 31.3 and 31.6 mole percent respectively. FIG. 2 contains the ¹HNMR spectrum of the polymer formed in run 5. Comparison of the ¹H NMRspectrum for comparison B polymer indicates a difference in the ratiosof the two peaks labled E and F. Using the respective integrated peakareas of the respective ¹H NMR spectra, the respective cluster indices(CI_(ES)) determined according to the following formula can becompared:.${CI}_{ES} = {{\left\lbrack \frac{{NMR}_{F}}{{NMR}_{E}} \right\rbrack \left\lbrack \frac{\left( {{4F_{1}} - 2} \right)}{\left( {1 - F_{1}} \right)} \right\rbrack}.}$

The calculations are as follows:${\text{Run~~5:~~~~~~~~~}{CI}_{ES}} = {{\left\lbrack \frac{30.539}{98.936} \right\rbrack \left\lbrack \frac{\left( {{4(0.687)} - 2} \right)}{\left( {1 - 0.687} \right)} \right\rbrack} = 0.74}$${{\text{Compare~~}\text{B}\text{:~~~~~}}{CI}_{ES}} = {{\left\lbrack \frac{42.6}{61.2} \right\rbrack \left\lbrack \frac{\left( {{4(0.684)} - 2} \right)}{\left( {1 - 0.684} \right)} \right\rbrack} = 1.62}$

It may be seen that the copolymer of the invention has a CI_(ES) of lessthan 1.0, whereas the comparative ES copolymer has a CI_(ES) of greaterthan 1.0, thereby indicating less uniform incorporation ofmonovinylaromatic monomer.

What is claimed is:
 1. A uniform, pseudo-random copolymer of ethyleneand a vinylaromatic monomer having a cluster index, CI_(ES) less than1.0 and a polymerized vinylaromatic monomer content less than 50 molepercent, wherein CI_(ES) is defined by the formula:${CI}_{ES} = {\left\lbrack \frac{{NMR}_{F}}{{NMR}_{E}} \right\rbrack \left\lbrack \frac{\left( {{4F_{1}} - 2} \right)}{\left( {1 - F_{1}} \right)} \right\rbrack}$

wherein F₁ is the mole fraction of ethylene in the polymer, NMR_(F) isthe integrated area of the peak of the ¹³C NMR spectrum of the copolymerassociated with vinylaromatic monomer/ethylene/vinylaromatic monomertriads appearing at approximately 25 to 26.9 pm, and NMR_(F) is theintegrated area of the peak of the ¹³C NMR spectrum of the copolymerassociated with triads containing onl a single incorporated vinylaromatic monomer appearing at approximately 27-29 ppm.
 2. The copolymerof claim 1 having a cluster index value less than 0.95 and a polymerizedvinylaromatic monomer content less than 47 mole percent.
 3. Thecopolymer of claims 1 or 2 wherein the vinylaromatic monomer is styrene.